Temperature-responsive molecular recognition chromatography using phenylalanine and tryptophan derived polymer modified silica beads

Yuki Hiruta, Ryosuke Kanazashi, Eri Ayano, Teruo Okano, Hideko Kanazawa

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Temperature-responsive polymers incorporating molecular-recognition sites were developed as stationary phases for high-performance liquid chromatography (HPLC). The grafted stationary phases consisted of functional copolymers composed of N-isopropylacrylamide (NIPAAm) and N-acryloyl aromatic amino acid methyl esters, i.e., phenylalanine and tryptophan methyl esters (Phe-OMe and Trp-OMe). Three novel temperature-responsive polymers, P(NIPAAm-co-Phe-OMe5), P(NIPAAm-co-Phe-OMe10), and P(NIPAAm-co-Trp-OMe5), were synthesized. These copolymers exhibited a reversible hydrophilic/hydrophobic phase transition at their lower critical solution temperatures (LCSTs). The polymers were grafted onto aminopropyl silica using an activated ester-amine coupling method, and were packed into a stainless steel column, which was connected to an HPLC system. Temperature-responsive chromatography was conducted using water as the sole mobile phase. More hydrophobic analytes were retained longer, and the retention times of aromatic steroids and aromatic amino acids were dramatically increased. This indicated that π-π interactions occurred between the phenyl or indole moieties of phenylalanine or tryptophan, respectively, and the aromatic compounds. Furthermore, the retention times of compounds with hydrogen bond acceptors were higher with P(NIPAAm-co-Trp-OMe5), which contained indole as a hydrogen bond donor, than with P(NIPAAm-co-Phe-OMe5). This indicated that hydrogen bonding occurred between the stationary phase and the analytes. These results indicate that hydrophobic, π-π, and hydrogen bonding interactions all affected the separation mode of the temperature-responsive chromatography, and led to selective separation with molecular recognition. Both temperature-response and molecular recognition characteristics are present in the proposed separation system that utilizes a temperature-responsive polymer bearing aromatic amino acid derivatives.

Original languageEnglish
Pages (from-to)910-917
Number of pages8
JournalAnalyst
Volume141
Issue number3
DOIs
Publication statusPublished - 2016 Feb 7

Fingerprint

Molecular recognition
Chromatography
Phenylalanine
Tryptophan
Silicon Dioxide
chromatography
Polymers
polymer
silica
Silica
Temperature
Aromatic Amino Acids
Hydrogen bonds
Carboxylic acids
hydrogen
ester
temperature
Amino acids
Esters
amino acid

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Electrochemistry
  • Biochemistry
  • Environmental Chemistry

Cite this

Temperature-responsive molecular recognition chromatography using phenylalanine and tryptophan derived polymer modified silica beads. / Hiruta, Yuki; Kanazashi, Ryosuke; Ayano, Eri; Okano, Teruo; Kanazawa, Hideko.

In: Analyst, Vol. 141, No. 3, 07.02.2016, p. 910-917.

Research output: Contribution to journalArticle

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